EP0554574A1 - Procédé de production d'un polymère de styrène et un catalyseur à utiliser dans ce procédé - Google Patents
Procédé de production d'un polymère de styrène et un catalyseur à utiliser dans ce procédé Download PDFInfo
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- EP0554574A1 EP0554574A1 EP92122164A EP92122164A EP0554574A1 EP 0554574 A1 EP0554574 A1 EP 0554574A1 EP 92122164 A EP92122164 A EP 92122164A EP 92122164 A EP92122164 A EP 92122164A EP 0554574 A1 EP0554574 A1 EP 0554574A1
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- carbon atoms
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- cyclopentadienyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Definitions
- the present invention relates to a process for producing a styrenic polymer and a catalyst for use therein. More particularly, it pertains to a process for efficiently producing a styrenic polymer having a high degree of syndiotactic configuration in the stereochemical structure of the polymer main chain and to a catalyst to be used in the process.
- a styrenic polymer having a syndiotactic configuration is obtained by polymerizing a styrenic monomer by the use of a catalyst comprising as primary ingredients a transition-metal compound, especially a titanium compound and an alkylaluminoxane (Refer to Japanese Patent Application Laid-Open Nos. 187708/1987, 179906/1988, 241009/1988, etc.).
- Methylaluminoxane particularly suitable as an alkylaluminoxane is obtained usually by the reaction between trimethylaluminum and water.
- the above-mentioned reaction involves the problem that the reaction is difficult to put into practical production because of its violent reaction, and further suffers the disadvantages that in addition to requiring expensive trimethylaluminum as the starting material, an excessively large amount of methylaluminoxane is required as a component of the catalyst as compared with the amount of a transition metal, thus causing an extremely expensive catalyst, and further that a large amount of residual ash component remains in the product resin.
- the present invention has been accomplished on the basis of the above-mentioned finding and information.
- the present invention provides a catalyst which comprises (A) a titanium compound represented by the general formula (I) TiR1XYZ (I) wherein R1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a halogen atom, or the general formula (II) Ti
- the present invention also provides a catalyst which comprises the above-mentioned components (A) and (B) and an alkylating agent.
- the present invention further provides a process for producing a styrenic polymer characterized by the use of the aforesaid catalyst in the case of polymerizing at least one styrenic monomer selected from styrene and a derivative thereof.
- the catalyst according to the present invention comprises as principal components the above-mentioned components (A) and (B), or the components (A), (B) and (C).
- the titanium compound that is, the component (A) of the catalyst
- the compound having one ⁇ electron-based ligand represented by the general formula (I) TiR1XYZ (I) wherein R1 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; and X, Y and Z, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a thioalkyl group having 1 to 20 carbon atoms, an ary group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or
- the substituted cyclopentadienyl group represented by R1 in the above formula is, for example, a cyclopentadienyl group substituted by at least one alkyl group having 1 to 6 carbon atoms, more specifically, methylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di(trimethylsilyl)-cyclopentadienyl group; 1,2,4-tri(trimethylsilyl)cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di(tert-butyl)cyclopentadienyl group; 1,2,4-(tert-butyl)cyclopentadienyl group; pentaalkylcyclopent
- Examples of the substituted indenyl group include methylindenyl group, dimethylindenyl group and trimethylindenyl group.
- examples of the substituted fluorenyl group include methylfluorenyl group.
- the above-mentioned compounds are desirable tetra-substituted cyclopentadienyl group and penta-substituted cyclopentadienyl group, and is particularly desirable pentamethylcyclopentadienyl group.
- X, Y and Z independently of one another, are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (specifically, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group and 2-ethylhexyl group), an alkoxy group having 1 to 12 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group and 2-ethylhexyloxy group, a thioalkoxy group having 1 to 20 carbon atoms (specifically, thiomethoxy group), an aryl group having 6 to 20 carbon atoms (specifically, phenyl group and naphthyl group), an aryloxy group having 6 to 20 carbon atoms (specifically, phenoxy group),
- titanium compounds represented by the general formula (I) include cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, 1,2,4-trimethylcyclopentadienyltrimethyltitanium, 1,2,3,4-tetramethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium, pentamethylcyclopentadienyltributyltitanium, cyclopent
- the mono[(substituted cyclopentadienyl]titanium compound may be the compound represented by the general formula (III) in which a cyclopentadienyl group is bonded to a metal via an arbitrary substituent group.
- R5 is a hydrogen atom, an alkyl group, an aryl group or a silyl group and may be the same or different
- J is an oxygen atom, a sulfur atom, NR6 or PR6 and is bonded to a cyclopentadienyl group via Q
- R6 is a hydrogen atom, an alkyl group, an aryl group or a silyl group
- Q is SiR72, CR72, SiR72SiR72, CR72CR72, SiR72SiR72SiR72 or CR72CR72
- R7 is a hydrogen atom, an alkyl group, an aryl group or a silyl group and may be the same or different
- a and B are each selected from a hydride, a halogen atom, an alkyl group, a silyl group, an aryl group, an amide group, an aryloxy group, an alkoxy group, a silyloxy group, a pho
- Another titanium compound that is, the component (A) of the catalyst, there is exemplified by the compound having two ⁇ electron-based ligands represented by the general formula (II) Ti(R2)2R3R4 (II) wherein R2 is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; R3 and R4 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a
- the substituted cyclopentadienyl group represented by R2 in the above formula is, for example, a cyclopentadienyl group substituted by at least one alkyl group having 1 to 6 carbon atoms, more specifically, methylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di(trimethylsilyl)cyclopentadienyl group; 1,2,4-tri(trimethylsilyl)cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di(tert-butyl)cyclopentadienyl group; 1,2,4-(tert-butyl)cyclopentadienyl group; pentaalkylcyclopenta
- Examples of the substituted indenyl group include methylindenyl group, dimethylindenyl group and trimethylindenyl group.
- examples of the substituted fluorenyl group include methylfluorenyl group.
- examples of the above-mentioned compounds are particularly desirable cyclopentadienyl group and substituted cyclopentadienyl group.
- Both or either of (R2)2 may be crosslinked by an alkylidene group having 1 to 5 carbon atoms, more specifically, methylidyne group; ethylidene group; propylidene group; dimethylcarbyl group or the like, or an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms, more specifically, dimethylsilyl group; diethylsilyl group; dibenzylsilyl group or the like; or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium atoms.
- an alkylidene group having 1 to 5 carbon atoms more specifically, methylidyne group; ethylidene group; propylidene group; dimethylcarbyl group or the like, or an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms, more specifically, dimethylsilyl group; diethylsilyl group; dibenz
- titanium compound represented by the general formula (II) include bis(cyclopentadienyl)dimethyltitanium; bis(cyclopentadienyl) diethyltitanium; bis(cyclopentadienyl)dipropyltitanium; bis(cyclopentadienyl)dibutyltitanium: bis(methylcyclopentadienyl)dimethyltitanium; bis(tert-butylcyclopentadienyl)dimethyltitanium; bis(1,3-dimethylcyclopentadienyl)dimethyltitanium; bis(1,3-di-tert-butylcyclopentadienyl)dimethyltitanium; bis(1,2,4-trimethylcyclopentadienyl)dimethyltitanium; bis(1,2,3,4-tetramethylcyclopentadienyl)dimethyltitanium; bis(cyclopentadie
- the compound may be a bidentate coordination complex such as 2,2'-thiobis(4-methyl-6-tert-butylphenyl)titanium diisopropoxide and 2,2'-thiobis(4-methyl-6-tert-butylphenyl)titanium dimethoxide.
- the component (B) of the catalyst according to the present invention is an ionic compound comprising a non-coordinate anion and a cation of an element typifying the group 4 elements of the Periodic Table.
- the non-coordinate anion include the anion represented by the general formula (IV) (M1X1X2 ---- X n ) (n-m)- (IV) wherein M1 is a metal selected from groups 5 to 15 of the Periodic Table; X1 to X n are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group (inclusive of halogen-substituted aryl group), having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a substituted alkyl group, an organometalloid group or
- M1 include B, Al, Si, P, As, Sb, etc.
- X1 to X n include a dialkylamino group such as dimethylamino and diethylamino; an alkoxyl group such as methoxy, ethoxy and n-butoxy; an aryloxy group such as phenoxy, 2,6-dimethylphenoxy and naphthyloxy; an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-octyl and 2-ethylhexyl; an aryl group having 6 to 20 carbon atoms, monoto penta-(fluoro)phenyl; an arylalkyl group having 7 to 20 carbon atoms such as benzyl; an alkylaryl group having 7 to 20 carbon atoms such as p-tolyl, 3,5-di(trifluoro
- anion is particularly desirable B(C6F5)4 ⁇ , that is tetra(pentafluorophenyl)borate.
- cation examples include triphenylcarbonium cation; 4,4',4''-tri(methoxyphenyl)-carbonium cation; 4,4'-di(methoxyphenyl)phenylcarbonium cation; tri(tolyl)carbonium cation; 4,4',4''-tri(chlorophenyl)carbonium cation; triphenylsilyl cation, trimethoxysilyl cation; tri(thioisopropyl)-silyl cation; trimethylsilyl cation; 4,4',4''-tri(methoxyphenyl)silyl cation; tri(tolyl)silyl cation and 4,4',4''-tri(chlorophenyl)silyl cation, among which is particularly desirable the cation in which M2 is C, that is, carbonium cation.
- the component (B) of the catalyst according to the present invention is an ionic compound comprising the above-mentioned non-coordinate anion and a cation of an element typifying the group 4 elements.
- ionic compound include triphenylcarbonium tetra(pentafluorophenyl)borate; 4,4',4''-tri(methoxyphenyl)carbonium tetra(pentafluorophenyl)borate; tri(tolyl)carbonium tetra(pentafluorophenyl)borate; 4,4', 4''-tri(chlorophenyl)carbonium tetra(pentafluorophenyl)borate; triphenylsilyl tetra(pentafluorophenyl)borate; trimethoxysilyl tetra(pentafluorophenyl)borate; tri(thioisopropyl)silyl tetra(pentaflu
- an alkylating agent as component (C).
- the above-mentioned compounds having an alkyl group are desirably aluminum compounds having an alkyl group, more desirably trialkylaluminium compounds and dialkylaluminum compounds.
- the compounds, that is, the components (C) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tir-n-butyl-aluminum, triisobutylaluminum and tir-tert-butylaluminum; dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride and di-tert-butylaluminum chloride; dialkylaluminum alkoxide such as dimethylalumin
- the catalyst according to the present invention comprises as the principal components the above-mentioned components (A) and (B), or the components (A), (B) and (C), and may be incorporated with a catalytic component in addition to the above components.
- the compounding ratios (A):(B) and (A):(B):(C) in the catalyst vary depending upon various conditions and can not be unequivocally defined. Under ordinary circumstances, however, the molar ratio of (A) to (B) is 1:10 to 10:1 and that of (A) to (C) is 1:0.01 to 1:1,000.
- the catalyst according to the present invention as described hereinbefore exhibits a high activity in the production of a styrenic polymer having a high degree of syndiotactic configuration.
- the present invention further provides a process for producing a styrenic polymer having a high degree of syndiotactic configuration by the use of the above-descirbed catalyst.
- a styrenic polymer according to the present invention is put into practice by polymerizing or copolymerizing at least one styrenic monomer selected from the group consisting of styrene and derivatives thereof such as an alkylstyrene, an alkoxystyrene, a halogenated styrene and a vinyl benzoate ester in the presence of the catalyst comprising as the principal the components (A) and (B) and, when necessary, the component (C).
- styrenic monomer selected from the group consisting of styrene and derivatives thereof such as an alkylstyrene, an alkoxystyrene, a halogenated styrene and a vinyl benzoate ester
- the catalyst according to the present invention is brought into contact with styrenic monomer/s by any one of the various methods including:
- reaction product of the components (A) and (B) may be isolated and purified in advance.
- the addition or contact of the above-mentioned components (A), (B) and (C) may be carried out at a temperature of 0 to 100°C and, needless to say, at the polymerization temperature.
- the polymerization of a styrenic monomer or monomers may be carried out by means of bulk polymerization or solution polymerization by the use of an aliphatic hydrocarbon solvent such as pentane, hexane or heptane, an alicyclic hydrocarbon solvent such as cyclohexane or an aromatic hydrocarbon solvent such as benzene, toluene or xylene.
- the polymerization temperature is not specifically limited, but is usually in the range of 0 to 90°C, preferably 20 to 70°C.
- the molecular weight of the styrenic polymer to be obtained can be effectively modified by means of polymerization reaction in the presence of hydrogen.
- the styrenic polymer thus obtained possesses a high degree of syndiotactic configuration.
- the styrenic polymer having a high degree of syndiotactic configuration means that its stereochemical structure is mainly of syndiotactic configuration, i.e. the stereostructure in which phenyl groups or substituted phenyl group as side chains are located alternately at opposite directions relative to the main chain consisting of carbon-carbon bonds. Tacticity is quantitavely determined by the nuclear magnetic resonance method (13C-NMR method) using carbon isotope.
- the tacticity as determined by the 13C-NMR method can be indicated in terms of proportions of structural units continuously connected to each other, i.e., a diad in which two sturctural units are connected to each other, a triad in which three structural units are connected to each other and a pentad in which five structural units are connected to each other.
- the styrenic polymers having a high degree of syndiotactic configuration means polystyrene, poly(alkylstyrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinylbenzoate), the mixtures thereof, and copolymers containing the above polymers as main components, having such a syndiotacticity that the proportion of racemic diad is at least 75%, preferably at least 85%, or the proportion of racemic pentad is at least 30%, preferably at least 50%.
- the poly(alkylstyrene) include poly(methylstyrene), poly(ethylstyrene) poly(isopropylstyrene), poly(tert-buthylstyrene), etc.
- poly(halogenated styrene) include, poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), etc.
- the poly(alkoxystyrene) include, poly(methoxystyrene), poly(ethoxystyrene), etc.
- the most desirable styrenic polymers are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and the copolymer of styrene and p-methylstyrene.
- the styrenic polymer obtained according to the process of the present invention is that with a high degree of syndiotacticity usually having a weight-average molecular weight of 10,000 to 10,000,000, preferably 100,000 to 5,500,000 with a number-average molecular weight of 5,000 to 5,500,000, preferably 50,000 to 2,500,000.
- the resultant polymer has a high degree syndiotactic configuration as such as described above, and a styrene polymer having an exceptionally high degree of syndiotacticity as well as an extremely high purity can be obtained by the steps of deashing treatment of the polymer thus obtained, as required, with a washing agent containing hydrochloric acid, etc.; additional washing; drying under reduced pressure; cleaning with a solvent such as methyl ethyl ketone for removing solubles therein; and treatment of the insolubles thus obtained by the use of chloroform, etc.
- the styrene polymer with a high degree of syndiotacticity has a melting point of 160 to 310°C and is surpassingly superior to the conventional styrenic polymer having an atactic configuration in terms of heat resistance.
- the catalyst according to the present invention is inexpensive as compared with the conventinoal catalysts comprising an aluminoxane as the primary component, exerts a high activity for the production of a styrenic polymer having a high degree of syndiotactic configuration and furthermore can reduce all of the residual metallic amounts in the course of the polymer production process, thereby enabling the simplification of the production process. According to the process of the present invention, therefore, a syndiotactic styrenic polymer can be obtained at a reduced production cost with enhanced efficiency.
- Lithium tetra(pentafluorophenyl)borate in an amount of 4.0 g was suspended in 50 mL of toluene.
- To the resultant suspension was added 1.97 g of triphenylcarbonium triborate in 250 mL of toluene in the form of slurry at room temperature.
- the toluene-soluble portion was filetered away, and the toluene-insoluble portion was washed with 100 mL of toluene and subjected to extraction with 40 mL of methylene chloride.
- the insoluble portion was filtered away and the filtrate was added dropwise to 500 mL of pentane to obtain a yellow objective product as the insoluble.
- the resultant polymer was cut into slices of 1 mm or less in thickness, which were subjected to Soxhlet extraction for 5 hours by the use of methyl ethyl keotne (MEK) as the extraction solvent.
- MEK methyl ethyl keotne
- SPS syndiotactic polystyrene
- Example 1 The procedure in Example 1 was repeated except that the components (A), (B) and (C) as indicated in Table 1 were employed. The characteristics and catalytic activities of SPS thus obtained are given in Table 1.
- Example 2 The procedure in Example 1 was repeated except that 30 ⁇ mol of triisobutylaluminum and 1.00 ⁇ mol of triphenylcarbonium tetra(pentafluorophenyl)borate was used. After the completion of the reaction, the reaction product was dried to afford 3.90 g of a polymer, which was subjected to Soxhlet extraction in the same manner as in Example 1. As the result, SPS was obtained as the raffinate at a yield of 3.83 g and a catalytic activity of 160.0 kg/g ⁇ Ti.
- Example 9 The procedure in Example 9 was repeated except that tri(p-chlorophenyl)carbonium tetra(pentafluorophenyl)borate solution was used in place of triphenylcarbonium tetra(pentafluorophenyl)borate solution.
- the reaction product was dried to give 3.86 g of a polymer, which was subjected to Soxhlet extraction in the same manner as in Example 1.
- SPS was obtained as the raffinate at a yield of 3.66 g and a catalytic activity of 153.0 kg/g ⁇ Ti.
- Example 11 The procedure in Example 11 was repeated except that di(p-methoxyphenyl)-phenylcarbonium tetra(pentafluorophenyl)borate solution was employed in place of tri(p-methoxyphenyl)carbonium tetra(pentafluorophenyl)borate solution. After the completion of the reaction, the reaction product was dried to give 6.67 g of a polymer, which was subjected to Soxhlet extraction in the same manner as in Example 1. AS the result, SPS was obtained as the raffinate at a yield of 6.45 g and a catalytic activity of 270.0 kg/g ⁇ Ti.
- Example 11 The procedure in Example 11 was repeated except that pentamethylcyclopentadienyl trimethoxide solution was employed in place of pentamethylcyclopentadienyltrimethyltitanium solution. After the completion of the reaction, the reaction product was dried to give 4.95 g of a polymer, which was subjected to Soxhlet extraction in the same manner as in Example 1. AS the result, SPS was obtained as the raffinate at a yield of 4.88 g and a catalytic activity of 204.0 kg/g ⁇ Ti.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP123192 | 1985-08-09 | ||
JP00123192A JP3194438B2 (ja) | 1992-01-08 | 1992-01-08 | スチレン系重合体の製造方法及びその触媒 |
JP1231/92 | 1992-01-08 |
Publications (2)
Publication Number | Publication Date |
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EP0554574A1 true EP0554574A1 (fr) | 1993-08-11 |
EP0554574B1 EP0554574B1 (fr) | 2001-03-07 |
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ID=11495702
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP92122164A Expired - Lifetime EP0554574B1 (fr) | 1992-01-08 | 1992-12-31 | Procédé de production d'un polymère de styrène et un catalyseur à utiliser dans ce procédé |
Country Status (5)
Country | Link |
---|---|
US (2) | US5461128A (fr) |
EP (1) | EP0554574B1 (fr) |
JP (1) | JP3194438B2 (fr) |
AT (1) | ATE199562T1 (fr) |
DE (1) | DE69231722T2 (fr) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994007927A1 (fr) * | 1992-10-05 | 1994-04-14 | Exxon Chemical Patents Inc. | Systeme catalyseur a productivite amelioree et son utilisation dans un procede de polymerisation |
WO1995029940A1 (fr) * | 1994-04-28 | 1995-11-09 | Exxon Chemical Patents Inc. | Catalyseurs cationiques et procede d'utilisation de ces catalyseurs |
EP0698619A1 (fr) * | 1993-03-31 | 1996-02-28 | Idemitsu Kosan Company Limited | Catalyseur pour la production de polymere vinylique et procede de production de polymere aromatique vinylique |
EP0705849A1 (fr) * | 1993-06-15 | 1996-04-10 | Idemitsu Kosan Company Limited | Procede de production de polymere olefinique, et catalyseur pour la polymerisation d'une olefine |
EP0707013A1 (fr) * | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Catalyseur de production d'un polymere de styrene et procede de production d'un polymere de styrene l'utilisant |
EP0707014A1 (fr) * | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Procede de production de copolymere a compose vinylique aromatique |
WO1996029353A1 (fr) * | 1995-03-17 | 1996-09-26 | Basf Aktiengesellschaft | Procede de preparation de polymerisats de composes vinyliques aromatiques sous pression en presence d'hydrocarbures tres volatils |
EP0751154A1 (fr) * | 1995-06-30 | 1997-01-02 | ENICHEM S.p.A. | Procédé de préparation d'un polymère vinylaromatique cristallin de structure principalement syndiotactique |
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US6291389B1 (en) | 1994-04-28 | 2001-09-18 | Exxonmobil Chemical Patents Inc. | Cationic polymerization catalysts |
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EP0640090B2 (fr) † | 1992-05-15 | 2007-11-28 | The Dow Chemical Company | Procede de preparation de composes a base de complexes metalliques de monocyclopentadienyle et procede d'utilisation |
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US5384299A (en) * | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5763549A (en) * | 1989-10-10 | 1998-06-09 | Fina Technology, Inc. | Cationic metallocene catalysts based on organoaluminum anions |
JP3216662B2 (ja) * | 1992-10-08 | 2001-10-09 | 出光興産株式会社 | スチレン系重合体の製造方法 |
JP3216748B2 (ja) * | 1993-07-23 | 2001-10-09 | 出光興産株式会社 | 芳香族ビニル化合物重合体組成物の製造触媒及びそれを用いた芳香族ビニル化合物重合体組成物の製造方法 |
JP3369294B2 (ja) * | 1994-03-11 | 2003-01-20 | 出光興産株式会社 | 遷移金属化合物、それを用いた重合用触媒及び該重合用触媒を用いたスチレン系重合体の製造方法 |
US5625087A (en) * | 1994-09-12 | 1997-04-29 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
JPH08134122A (ja) * | 1994-11-11 | 1996-05-28 | Idemitsu Kosan Co Ltd | 重合用触媒及びそれを用いたスチレン系重合体の製造方法 |
WO1997019959A1 (fr) * | 1995-11-27 | 1997-06-05 | The Dow Chemical Company | Catalyseur sur support contenant un activateur de formation de cations amarres |
US5644009A (en) * | 1995-11-27 | 1997-07-01 | Industrial Technology Research Institute | Catalyst composition for preparing high syndiotacticity polystyrene from styrene of other arylethylene monomers and processes using the same |
US5895771A (en) * | 1997-06-05 | 1999-04-20 | Akzo Nobel Nv | Fluorinated alkoxy and/or aryloxy aluminates as cocatalysts for metallocene-catalyzed olefin polymerizations |
DE19757540A1 (de) * | 1997-12-23 | 1999-06-24 | Hoechst Ag | Geträgertes Katalysatorsystem zur Polymerisation von Olefinen |
US6232414B1 (en) | 1999-03-31 | 2001-05-15 | Phillips Petroleum Company | Process to make a monovinylaromatic polymer and said monovinylaromatic polymer |
JP2002179714A (ja) * | 2000-12-12 | 2002-06-26 | Idemitsu Petrochem Co Ltd | 重合体混合物の製造方法 |
JP6704808B2 (ja) * | 2016-07-05 | 2020-06-03 | 株式会社Adeka | 薄膜形成用原料及び薄膜の製造方法 |
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1992
- 1992-01-08 JP JP00123192A patent/JP3194438B2/ja not_active Expired - Fee Related
- 1992-12-31 DE DE69231722T patent/DE69231722T2/de not_active Expired - Fee Related
- 1992-12-31 EP EP92122164A patent/EP0554574B1/fr not_active Expired - Lifetime
- 1992-12-31 AT AT92122164T patent/ATE199562T1/de not_active IP Right Cessation
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1993
- 1993-01-04 US US08/000,213 patent/US5461128A/en not_active Expired - Fee Related
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1995
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EP0427696A2 (fr) * | 1989-10-10 | 1991-05-15 | Fina Technology, Inc. | Procédé et catalyseur pour produire des polymères syndiotactiques |
EP0426637B1 (fr) * | 1989-10-30 | 1995-04-05 | Fina Technology, Inc. | Préparation de catalyseurs métallocènes pour la polymérisation d'oléfines |
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EP0640090B2 (fr) † | 1992-05-15 | 2007-11-28 | The Dow Chemical Company | Procede de preparation de composes a base de complexes metalliques de monocyclopentadienyle et procede d'utilisation |
WO1994007927A1 (fr) * | 1992-10-05 | 1994-04-14 | Exxon Chemical Patents Inc. | Systeme catalyseur a productivite amelioree et son utilisation dans un procede de polymerisation |
EP0698619A1 (fr) * | 1993-03-31 | 1996-02-28 | Idemitsu Kosan Company Limited | Catalyseur pour la production de polymere vinylique et procede de production de polymere aromatique vinylique |
US5858904A (en) * | 1993-03-31 | 1999-01-12 | Idemitsu Kosan Co., Ltd. | Catalyst for production of vinyl-based polymer and process for production of vinyl-based aromatic polymer |
EP0698619A4 (fr) * | 1993-03-31 | 1996-06-12 | Idemitsu Kosan Co | Catalyseur pour la production de polymere vinylique et procede de production de polymere aromatique vinylique |
EP0705849A4 (fr) * | 1993-06-15 | 1996-10-23 | Idemitsu Kosan Co | Procede de production de polymere olefinique, et catalyseur pour la polymerisation d'une olefine |
EP0705849A1 (fr) * | 1993-06-15 | 1996-04-10 | Idemitsu Kosan Company Limited | Procede de production de polymere olefinique, et catalyseur pour la polymerisation d'une olefine |
US6462154B1 (en) | 1993-06-15 | 2002-10-08 | Idemitsu Kosan Co., Ltd. | Process for preparing olefin polymer and catalyst for polymerization of olefin |
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EP0707013A4 (fr) * | 1993-07-02 | 1996-06-12 | Idemitsu Kosan Co | Catalyseur de production d'un polymere de styrene et procede de production d'un polymere de styrene l'utilisant |
EP0707014A1 (fr) * | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Procede de production de copolymere a compose vinylique aromatique |
US5747613A (en) * | 1993-07-02 | 1998-05-05 | Idemitsu Kosan Co., Ltd. | Process for producing aromatic vinyl compound-based copolymer |
EP0707014A4 (fr) * | 1993-07-02 | 1996-06-12 | Idemitsu Kosan Co | Procede de production de copolymere a compose vinylique aromatique |
KR100266114B1 (ko) * | 1994-04-28 | 2000-09-15 | 엣킨슨 죠지 에이치 | 양이온 촉매 및 이 촉매를 사용하는 방법 |
WO1995029940A1 (fr) * | 1994-04-28 | 1995-11-09 | Exxon Chemical Patents Inc. | Catalyseurs cationiques et procede d'utilisation de ces catalyseurs |
US6699938B2 (en) | 1994-04-28 | 2004-03-02 | Exxonmobil Chemical Patents Inc. | Cationic catalysts and process for using said catalysts |
US6291389B1 (en) | 1994-04-28 | 2001-09-18 | Exxonmobil Chemical Patents Inc. | Cationic polymerization catalysts |
WO1996029353A1 (fr) * | 1995-03-17 | 1996-09-26 | Basf Aktiengesellschaft | Procede de preparation de polymerisats de composes vinyliques aromatiques sous pression en presence d'hydrocarbures tres volatils |
US5629391A (en) * | 1995-06-30 | 1997-05-13 | Enichem S.P.A. | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure |
EP0751154A1 (fr) * | 1995-06-30 | 1997-01-02 | ENICHEM S.p.A. | Procédé de préparation d'un polymère vinylaromatique cristallin de structure principalement syndiotactique |
US5952430A (en) * | 1996-09-24 | 1999-09-14 | Shell Oil Company | Process for selective hydrogenation of poly(monovinyl aromatic)-poly(conjugated diene) block copolymers |
EP0830895A1 (fr) * | 1996-09-24 | 1998-03-25 | Shell Internationale Researchmaatschappij B.V. | Catalyseur à base d'un complexe métallique du Ti, Zr ou Hf et procédé d'hydrogénation d'oléfines ou de polymères |
CN1055096C (zh) * | 1997-09-03 | 2000-08-02 | 中国石油化工总公司 | 制备苯乙烯间规聚合物的催化剂 |
CN1055097C (zh) * | 1997-09-03 | 2000-08-02 | 中国石油化工总公司 | 制备间规聚苯乙烯的催化剂 |
WO2000000523A1 (fr) * | 1998-06-30 | 2000-01-06 | The Dow Chemical Company | Procede ameliore de polymerisation syndiotactique de monovinylidene aromatique |
WO2000015676A1 (fr) * | 1998-09-16 | 2000-03-23 | Univation Technologies, Llc | Composition catalytique monocyclopentadienyle/métal pour polymérisation d'oléfines |
AU756439B2 (en) * | 1998-11-13 | 2003-01-16 | Univation Technologies Llc | Nitrogen-containing Group 13 anionic complexes for olefin polymerization |
US6479424B1 (en) | 1998-12-14 | 2002-11-12 | Bp Corporation North America Inc. | Fluxional catalysts and related ligands containing bulky substituents |
Also Published As
Publication number | Publication date |
---|---|
DE69231722D1 (de) | 2001-04-12 |
ATE199562T1 (de) | 2001-03-15 |
JP3194438B2 (ja) | 2001-07-30 |
JPH05186527A (ja) | 1993-07-27 |
EP0554574B1 (fr) | 2001-03-07 |
US5461128A (en) | 1995-10-24 |
US5543481A (en) | 1996-08-06 |
DE69231722T2 (de) | 2001-06-21 |
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